Siloxane derivatives, producing method thereof and agents including siloxane derivative

ABSTRACT

Novel siloxane derivatives represented by general formula (1): &lt;IMAGE&gt; (1)  A method for producing the siloxane derivatives and agents such as cosmetic preparations, emulsifying dermatotherapeutic external agents and the like including at least one of the siloxane derivatives are also disclosed.

This is a division of application Ser. No. 08/193,746, filed Feb. 9,1994, now abandoned which is a division of Ser. No. 07/926,186, filedAug. 7, 1992, now U.S. Pat. No. 5,306,838, granted Apr. 26, 1994, whichis a continuation of application Ser. No. 07/750,535 filed Aug. 27,1991, now U.S. Pat. No. 5,144,054, granted Sep. 1, 1992.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to novel siloxane derivatives havingsurface active action useful as an emulsifier, a method for producingthe novel siloxane derivatives, and agents including a novel siloxanederivative such as cosmetic preparations, emulsifying dermatotherapeuticexternal agents making use thereof and the like.

2. Description of the Background Art

Conventionally, siloxane compounds having surface active action aredivided into four groups such as compounds having an anionic hydrophilicgroup, compounds having a cationic hydrophilic group, compounds having abetaine hydrophilic group and compounds having a nonionic hydrophilicgroup according to kinds of denatured hydrophilic groups.

As to the compounds having a nonionic hydrophilic group, polyoxyalkylenedenatured silicone surfactants having a polyoxyalkylene group as ahydrophilic group are known. However, these are inferior in emulsifyingstability, and, when it is used as an emulsifier such as cosmeticpreparations or the like, in order to obtain sufficient emulsifyingstability, a thickener or thickeners such as silica, clay mineral andthe like must be further added to.

On the other hand, a polyalcoholic hydroxyl group as the nonionichydrophilic group excepting the polyoxyalkylene group can be thought of,but now silicone surfactants having a polyalcoholic hydroxyl group as ahydrophilic group are hardly known except that a polyglycerin denaturedsilicone disclosed in Japanese patent publication No. Sho 62-34039 and asorbitan denatured silicone disclosed in Japanese patent laid-open No.Sho 57-209295 are known so as to exhibit the surface active action.

Further, silicone compounds denatured by a glyceryl group as apolyalcoholic hydroxyl group are known, as disclosed in Japanese patentlaid-open Nos. 62-195389, 64-16793 and 63-101388, but these compoundsare surface modifiers making use of reactivity of the hydroxyl group forsynthetic resins, and their surface active actions are unknown.

As described above, there is practically nothing at all of nonionicsilicone surfactant having sufficient capability up to now.

In the meantime, conventionally, water-in-oil type emulsifyingdermatotherapeutic external agents represented by water-in-oil typeemulsifying cosmetic preparations have been widely used in virtue oftheir excellent properties such as good fitness to a skin due to a filmformed on a skin surface, good cosmetic adhesiveness and the like.

However, on the contrary, the water-in-oil type emulsifyingdermatotherapeutic external agents have drawbacks such as bad slip onapplying, strong oiliness and stickiness feelings and the like. Hence,recently, silicone oils as an oil solution having less sticky or plainand smooth usage feelings and excellent water repellency have beenmostly used, but it is difficult to emulsify the silicone oils and thusextremely difficult to obtain an emulsifying system having excellentstability.

Therefore, it has been desired to develop novel emulsifiers capable ofstably emulsifying not only usual oil solutions but also silicone oilsand giving good usage feeling when applying on a skin.

SUMMARY OF THE INVENTION

Accordingly, it is an object of the present invention to provide novelsiloxane derivatives having surface active action useful as anemulsifier capable of realizing excellent emulsification stability andhaving good fitness, good slip, good cosmetic adhesiveness, good usagefeeling.

It is another object of the present invention to provide a method forproducing novel siloxane derivatives having surface active action usefulas an emulsifier capable of realizing excellent emulsification stabilityand having good fitness, good slip, good cosmetic adhesiveness, goodusage feeling.

It is further object of the present invention to provide agents such ascosmetic preparations and emulsifying dermatotherapeutic external agentsincluding a novel siloxane derivative having surface active actionuseful as an emulsifier capable of realizing excellent emulsificationstability and having good fitness, good slip, good cosmeticadhesiveness, good usage feeling.

In accordance with one aspect of the present invention, there isprovided a siloxane derivative represented by general formula (1)##STR2## wherein at least one of R¹ to R¹² is a group represented bygeneral formula (2) ##STR3## wherein Q is a divalent hydrocarbon grouphaving 3 to 20 carbon atoms, R¹³ and R¹⁴ are hydrogen atom or ahydrocarbon group having 1 to 5 carbon atoms, and at least one of R¹³and R¹⁴ is hydrogen atom: the remainings of R¹ to R¹² arestraight-chain, branched-chain or cyclic hydrocarbon groups having 1 to30 carbon atoms or groups represented by general formula (3)

    --X--R.sup.15                                              ( 3)

wherein X is a divalent hydrocarbon group having an ether bonding and/orester bonding and R¹⁵ is a straight-chain, branched-chain or cyclichydrocarbon group having 1 to 30 carbon atoms; l, m and n are numbers of0 to 2,000, and at least one of R¹ to R³ and R¹⁰ to R¹² is a grouprepresented by general formula (2) when l+m+n=0 except that one of R¹ toR¹² is a group represented by general formula (2) wherein Q istrimethylene and R¹³ and R¹⁴ are both hydrogen atoms; and the remainingsof R¹ to R¹² are all methyl groups.

In a preferable siloxane derivative, Q is an alkylene group having 3 to20 carbon atoms and R¹³ and R¹⁴ are hydrogen atoms, and wherein R¹ toR¹² are alkyl groups having 1 to 30 carbon atoms.

In the siloxane derivative, l+m+n can be 0 to 2,000 and Q can be analkylene group having 3 to 20 carbon atoms.

Further preferable siloxane derivatives are represented by generalformulas (1A) to (1D) ##STR4##

In accordance with another aspect of the present invention, there isprovided a method for producing a siloxane derivative represented bygeneral formula (1a) ##STR5## wherein at least one of R^(1') to R^(12')represents a group represented by general formula (2), the remainings ofR^(1') to R^(12') are straight-chain, branched-chain or cyclichydrocarbon groups having 1 to 30 carbon atoms, and at least one ofR^(1') to R^(3') and R^(10') to R^(12') represents a group representedby general formula (2) when l+m+n=0 except that one of R^(1') to R^(12')represents a group represented by general formula (2) wherein Qrepresents trimethylene and R¹³ and R¹⁴ represent both hydrogen atoms,and the remainings of R¹ to R¹² represent all methyl groups, comprisingreacting a compound represented by general formula (4) ##STR6## whereinat least one of R¹⁶ to R²⁷ represents hydrogen atom, the remainings ofR¹⁶ to R²⁷ represent a straight-chain, branched-chain or cyclichydrocarbon group having 1 to 30 carbon atoms, l, m and n are numbers of0 to 2000, and at least one of R¹⁶ to R¹⁸ and R²⁵ to R²⁷ representshydrogen atom when l+m+n=0, with a compound represented by generalformula (2') ##STR7## In formula (2'), Q' represents a hydrocarbon grouphaving 3 to 20 carbon atoms and one double bond, and R¹³ and R¹⁴ are thesame as described above.

In accordance with further aspect of the present invention, there isalso provided a method for producing a siloxane derivative representedby general formula (1b) ##STR8## wherein at least one of R^(1") toR^(12") represents a group represented by general formula (2), at leastone of the remainings of R^(1") to R^(12") represents a grouprepresented by general formula (3), and the remainings of R^(1") toR^(12") are straight-chain, branched-chain or cyclic hydrocarbon groupshaving 1 to 30 carbon atoms, and, when l+m+n=0, at least one of R^(1")to R^(3") and R^(10") to R^(12") represents a group represented bygeneral formula (2) and at least one of the remainings of R^(1") toR^(3") and R^(10") to R^(12") represents a group represented by generalformula (3), comprising reacting a compound represented by generalformula (4') ##STR9## wherein at least two of R^(16') to R^(27')represent hydrogen atoms, the remainings of R^(16') to R^(27') representa straight-chain, branched-chain or cyclic hydrocarbon group having 1 to30 carbon atoms, l, m and n are the same as described above, and atleast two of R^(16') to R^(18') and R^(25') to R^(27') representhydrogen atoms when l+m+n=0, with compounds represented by generalformulas (2') and (3')

    X'--R.sup.18                                               ( 3')

wherein X' is a hydrocarbon group having at least one double bond and anether bonding and/or ester bonding and R¹⁵ is the same as describedabove.

The siloxane derivative represented by general formula (1) is used as anemulsifier.

A cosmetic preparation includes a siloxane derivative represented bygeneral formula (1).

A emulsifying dermatotherapeutic external agent includes (A) 5 to 70weight % of oil phase component: (B) 20 to 94.9 weight % of water phasecomponent; and (C) 0.1 to 30 weight % of emulsifier including a siloxanederivative represented by general formula (1).

In a preferable emulsifying dermatotherapeutic external agent, the oilphase component (A) includes at most 50 weight % of silicone oil, and inthe siloxane derivative of the component (C), l+m+n is 0 to 2,000, and Qis an alkylene group having 3 to 20 carbon atoms.

In another preferable emulsifying dermatotherapeutic external agent, theoil phase component (A) includes 50 weight % of silicone oil, and thesiloxane derivative in the component (C) is represented by eithergeneral formula (1A)

DETAILED DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENTS

The present invention will now be described in detail with reference toExamples thereof.

Under the actual circumstances, researches have been carried out to findthat novel siloxane derivatives having a glyceryl group, as hereinafterdescribed in detail, are suitable nonionic surfactants as emulsifiers ofcosmetic preparations, dermatotherapeutic external agents and the liketo bring about the completion of the present invention.

That is, according to the present invention, there are provided novelsiloxane derivatives represented by general formula (1), a method forproducing the siloxane derivatives and agents such as cosmeticpreparations, emulsifying dermatotherapeutic external agents and thelike including at least one of the siloxane derivatives: In generalformula (1), at least one of R¹ to R¹² is a group represented by generalformula (2) ##STR10## wherein Q is a divalent hydrocarbon group having 3to 20 carbon atoms, R¹³ and R¹⁴ are hydrogen atom or a hydrocarbon grouphaving 1 to 5 carbon atoms, and at least one of R¹³ and R¹⁴ is hydrogenatom; the remainings of R¹ to R¹² are straight-chain, branched-chain orcyclic hydrocarbon groups having 1 to 30 carbon atoms or groupsrepresented by general formula (3)

    --X--R.sup.15                                              (3)

wherein X is a divalent hydrocarbon group having an ether bonding and/orester bonding and R¹⁵ is a straight-chain, branched-chain or cyclichydrocarbon group having 1 to 30 carbon atoms; l, m and n are numbers of0 to 2,000, and at least one of R¹ to R³ and R¹⁰ to R¹² is a grouprepresented by general formula (2) when l+m+n=0 except that one of R¹ toR¹² is a group represented by general formula (2) wherein Q istrimethylene and R¹³ and R¹⁴ are both hydrogen atoms; and the remainingsof R¹ to R¹² are all methyl groups.

In general formula (2), as to the divalent hydrocarbon group having 3 to20 carbon atoms, represented by Q, an alkylene group having 3 to 20hydrogen atoms is preferable, and more specifically, for example,straight-chain alkylene such as trimethylene, tetramethylene,pentamethylene, hexamethylene, heptamethylene, octamethylene,nonamethylene, decamethylene, undecamethylene, dodecamethylene,tetradecamethylene, hexadecamethylene, octadecamethylene or the like,branched-chain methylene such as propylene, 2-methyltrimethylene,2-methyltetramethylene, 2-methylphetamethylene, 3-methylpentamethyleneor the like are given. Regarding the hydrocarbon group having 1 to 5carbon atoms, represented by R¹³ and R¹⁴, straight-chain, branched-chainor cyclic alkyl groups such as methyl group, ethyl group, propyl group,butyl group, pentyl group, isopropyl group, sec-butyl group, t-butylgroup, neopentyl group, cyclopentyl group and the like are given.

In general formula (3), as regards the divalent hydrocarbon group havingthe ether bonding and/or ester bonding, represented by X, --(CH₂)r--(OC₂H₄)p--(OC₃ H₆)q--O-- wherein r is integer of 3 to 20 and p and q arenumber of 0 to 50, --(OCH₂)_(r) --O--CO--, --(OCH₂)_(r) --COO-- and thelike are given. As to the straight-chain, branched-chain or cyclichydrocarbon group having 1 to 30 carbon atoms, represented by R¹⁵,straight-chain alkyl groups such as methyl group, ethyl group, propylgroup, butyl group, pentyl group, hexyl group, octyl group, decyl group,dodecyl group, tetradecyl group, hexadecyl group, octadecyl group,eicocyl group, dococyl group, tetracocyl group, hexacocyl group,octacocyl group, triacontyl group and the like; branched-chain alkylgroups such as isopropyl group, sec-butyl group, t-butyl group,neopentyl group, 1-ethylpropyl group, 1-heptyldecyl group and the like;and cyclic alkyl groups such as cyclopentyl group, cyclohexyl group,abietyl group, cholesteryl group and the like are given. As to l, m andn, a range of 0 to 2000 is preferable in view of availability of rawmaterials of organohydrogen polysiloxanes, operability in manufacturingand the like.

In the siloxane compounds represented by general formula (1), a compoundor compounds in which Q in general formula (2) represented by at leastone of R¹ to R¹² is an alkylene group having 3 to 30 carbon atoms, R¹³and R¹⁴ are both hydrogen atoms, and the remainings of R¹ to R¹² arealkylene groups having 1 to 30 carbon atoms can be preferably inparticular.

In the siloxane compounds represented by general formula (1), morepreferable compounds are shown by formulas (1A), (1B), (1C) and (1D) asfollows. ##STR11## In this formula, R^(2A) represents an alkyl grouphaving 2 to 30 carbon atoms and s is a number of 3 to 20. ##STR12## Inthis formula, t is a number of 0 to 2000 and u is a number of 3 to 20.##STR13## In this formula, t is a number of 0 to 2000 and s is a numberof 3 to 20. ##STR14## In this formula, R^(4D) represents an alkyl grouphaving 2 to 30 carbon atoms, t and v are numbers of 0 to 1000, w is anumber of 1 to 1000, and s is a number of 3 to 20.

According to the present invention, the siloxane compounds representedby general formula (1) can be prepared in accordance with reactionschemes as follows.

(i) Preparation of a siloxane compound (1a) having no group representedby general formula (3) from compounds (4) and (2'). ##STR15## In formula(4), at least one of R¹⁶ to R²⁷ represents hydrogen atom, the remainingsof R¹⁶ to R²⁷ represent a straight-chain, branched-chain or cyclichydrocarbon group having 1 to 30 carbon atoms, l, m and n are numbers of0 to 2000, and at least one of R¹⁶ to R¹⁸ and R²⁵ to R²⁷ representshydrogen atom when l+m+n=0. In formula (2'), Q' represents a hydrocarbongroup having 3 to 20 carbon atoms and one double bond, and R¹³ and R¹⁴are the same as described above. In formula (1a), at least one of R^(1')to R^(12") represents a group represented by general formula (2), theremainings of R^(1') to R^(12') are straight-chain, branched-chain orcyclic hydrocarbon groups having 1 to 30 carbon atoms, and at least oneof R^(1') to R.sup. 3' and R^(10') to R^(12') represents a grouprepresented by general formula (2) when l+m+n=0 except that one ofR^(1') to R^(12') represents a group represented by general formula (2)wherein Q represents trimethylene and R¹³ and R¹⁴ represent bothhydrogen atoms, and the remainings of R¹ to R¹² represent all methylgroups.

That is, an organohydrogen polysiloxanes (4) having at least onesilicon-hydrogen bonding is reacted with an alkenylglyceryl ether (2')to obtain a siloxane derivative (1a) having no group represented bygeneral formula (3). (ii) Preparation of a siloxane compound (1b) havinga group represented by general formula (3) from compounds (4'), (2') and(3'). ##STR16## In formula (4'), at least two of R^(16') to R^(27')represent hydrogen atoms, the remainings of R^(16') to R^(27') representa straight-chain, branched-chain or cyclic hydrocarbon group having 1 to30 carbon atoms, l, m and n are the same as described above, and atleast two of R^(16') to R^(18') and R^(25') to R^(27') representhydrogen atoms when l+m+n=0. In formula (2'), Q', R¹³ and R¹⁴ are thesame as described above. In formula (3'), X' is a hydrocarbon grouphaving at least one double bond and an ether bonding and/or esterbonding and R¹⁵ is the same as described above. In formula (1b), atleast one of R^(1") to R^(12") represents a group represented by generalformula (2), at least one of the remainings of R^(1") to R^(12")represents a group represented by general formula (3), and theremainings of R^(1") to R^(12") are straight-chain, branched-chain orcyclic hydrocarbon groups having 1 to 30 carbon atoms, and, whenl+m+n=0, at least one of R^(1") to R^(3") and R^(10") to R^(12")represents a group represented by general formula (2) and at least oneof the remainings of R^(1") to R^(3") and R^(10") to R^(12") representsa group represented by general formula (3).

That is, an organohydrogen polysiloxane (4') having at least twosilicon-hydrogen bondings is reacted with an alkenylglyceryl ether (2')and a compound (3') to obtain a siloxane derivative (1b) having a grouprepresented by general formula (3). In this case, any of compounds (2')and (3') can be firstly reacted with compound (4'), or both compounds(2') and (3') can be reacted with compound (4') at the same time.

The organohydrogen polysiloxane (4) or (4') of the raw materialessentially includes at least one [(4)] or two [(4')] silicon-hydrogenbonding or bondings in the molecule, but there is no further limitationin its viscosity, molecular structure and so forth. Hence, various kindsof known polysiloxanes can be used, but as to l, m and n, a range of 0to 2000 is preferable in view of availability of raw materials oforganohydrogen polysiloxanes, operability in manufacturing and the like.

As to compound (2'), a compound represented by general formula (2')wherein Q' is an ω-alkenyl group is preferable. Regarding compound (3'),a compound represented by general formula (3') wherein X' isCH2═CHCH2--(OC2H4)p--(OC3H6)q--O-- (p and q are the same as describedabove), CH2═CH--(CH2)r'--O--CO-- (r' is an integer of 1 to 18),CH2═CH--(CH2)r'--CO--O-- (r' is the same as above), or the like ispreferable.

In the above-described preparations (i) and (ii), the reaction iscarried out in the presence of a catalyst. As examples of the catalyst,catalysts usually used in a hydrosililation, for example, a free radicalinitiator: photo-initiator: complex compounds of a metal such asruthenium, rhodium, palladium, asmium, iridium, platinum or the like:these carried on a silica gel or alumina; and the like can be given. Inparticular, platinic chloride, Speier's reagent (isopropyl alcoholsolution of platinic chloride) or the like are preferable. An amount ofthe catalyst used is a sufficient amount for promoting the reaction ofthe organohydrogen polysiloxane (4) or (4') with the alkenylglycerylether (2') and/or the compound (3') and thus is not restricted. Apreferable amount the catalyst is a range of 10⁻⁶ to 10⁻¹ mol per 1 molof olefin used.

In the reaction, a use of a reaction solvent is not essential, but thereaction can be run in a suitable solvent if necessary. As regards thereaction solvent, it is not limited in particular as long as it does notinhibit the reaction, for example, hydrocarbon solvents such as pentane,hexane, cyclohexane and the like; benzene series solvents such asbenzene, toluene, xylene and the like; ether solvents such as diethylether, diisopropyl ether and the like; alcohol solvents such asmethanol, ethanol, isopropanol, butanol and the like; and the like canbe given. When the alcohol solvent is used, a pH regulator such aspotassium acetate or the like is preferably used for preventing orinhibiting a dehydrogenation reaction between Si--H and --OH, asdisclosed in Japanese patent laid-open No. Sho 57-149290.

Relating to the amount of the alkenylglyceryl ether (2') and/or thecompound (3') with reference to the organohydrogen polysiloxane (4) and(4') used in this reaction, as long as a sufficient amount ofalkenylglyceryl ether (2') for including at least one silicon-connectedglyceryl group (2) in the molecule of the obtained siloxane derivativeis present, any amount of the other compound is used. However, when anoil solution of carbon system is emulsified by using the obtainedcompound (1), the sum unit number of the groups (2) and (3) is equal toor more than that of the remaining siloxanes. When an oil solution ofsilicon system is emulsified by using the obtained compound (1), the sumunit number of the groups (2) and (3) is preferably in a range of atmost 1/5 of that of the remaining siloxanes.

The hydrosililation is run at 0° C. to 200° C., preferably 0° C. to 100°C. in consideration of the reaction speed, coloring of the obtainedcompound and so forth. The reaction time is preferably approximately 0.5to 24 hours.

Thus the obtained siloxane derivatives (1) according to the presentinvention can be preferably used as components for cosmeticpreparations, particularly emulsifiers. The formulations and kinds ofthe applicable cosmetic preparations can not be limited in particular,for instance, skin care cosmetic preparations such as milk lotion orliquid cream, lotion, foundation and the like; hair care cosmeticpreparations such as shampoo, rinse, treatment and the like are given. Amixing amount of the siloxane derivative (1) of the present invention inthe cosmetic preparation can not be also limited in particular, butusually a preferable amount is 0.001 to 90% by weight, more preferably 1to 50% by weight in particular.

As described above, the siloxane derivatives (1) are useful asemulsifiers and can be mixed in a variety of emulsifying systems, and,when the siloxane derivatives are used in emulsifying dermatotherapeuticexternal agents in particular, stable external agents having good usagefeeling can be obtained. Their preferable composition is as follows.

(A) oil phase component: 5 to 70 weight %, particularly preferably 10 to50 weight %;

(B) water phase component: 20 to 94.9 weight %, particularly preferably50 to 90 weight %; and

(C) emulsifier including a siloxane derivative (1): 0.1 to 30 weight %,particularly preferably 0.5 to 30 weight %.

As to the oil phase component (A) used in the emulsifyingdermatotherapeutic external agents, for example, silicone oils:hydrocarbons such as squalene, liquid paraffin, vaseline and the like;waves such as spermaceti, carnauba was and the like; ester oils such asjojoba oil, octyldodecyl myristate, neopentyl dioctanoate glycol and thelike; natural animal or vegetable oils such as olive oil, macademia nutoil and the like; diglyceride and the like can be given. In these oils,as examples of the silicone oils, oils usually used in cosmeticpreparations can be used, for example, dimethyl polysiloxane,dimethylcyclo polysiloxane, methylphenyl polysiloxane, methylhydrogenpolysiloxane and the like can be given. Particularly, in order to reduceoiliness feeling and stickiness feeling, volatile dimethyl polysiloxane,dimethylcyclo polysiloxane and the like can be preferably exemplified.These oil solutions can be used independently or at least two kinds ofthe oil solutions can be used in combination.

The main ingredient (at least 50 weight %, and particularly at least 70weight %) of the oil phase component (A) is the silicone oil, theobtained emulsifying dermatotherapeutic external agents possess plainusage feeling, and its emulsifying system is stable. In case that thesilicone oil is the main ingredient as the oil phase component, asiloxane derivative represented by general formula (A) wherein l+m+n=0to 2000, and Q is an alkylene group having 3 to 20 carbon atoms can bepreferably used as the emulsifiers in particular.

Further, when the main ingredient of the oil phase component (A) is anoil solution except the silicone oils, preferably, the compound (1A) or(1D) can be used in view of the stability. When the compound (1D) isused, excellent external agents having no stimulus can be obtained.

As examples of the water phase component (B), for example, in additionto water, alcohols, polyols, inorganic salts, organic salts and the likecan be given. In these components, the polyols are particularly usefulbecause of wet-holding or humidifying property. Such polyols include,for example, propylene glycol, isoprene glycol (manufactured by KurareCompany), 1,3-butylene glycol, dipropylene glycol, glycerol, diglycerol,triglycerol, polyglycerol, trimethylolpropane, erythritol,pentaerythritol, sorbitan, sorbitol, glucose, maltitol, succharose,trehalose, ethylene oxide or propylene oxide adducts of sugar or sugarderivatives, polyethyleneglycol and the like. In particular, ethyleneoxide adducts of the sugar derivatives such as glycerol, sorbitol,maltitol, polyoxyethylenemethyl glucoside and the like are preferable.These can be used independently or in combination. The mixing amount ofthe polyol is different depending on humidifying property, usagefeeling. consistency and the like of the dermatotherapeutic externalagents to be obtained, and, when an amount of 30 to 90 weight %,particularly 40 to 65 weight % of the polyol is mixed in the waterphase, a difference of its refractive index with reference to the oilphase becomes small, and the appearance of the dermatotherapeuticexternal agents can be made to be semitransparent or transparent.

As to the inorganic salts or the organic salts, those having asolubility of at least 0.2 g/100 g of water at 20° C. are preferable.Such inorganic and organic salts include, for example, alkali metalsalts, alkaline earth metal salts or aluminum salts of inorganic acidssuch as hydrochloric acid, sulfuric acid, nitric acid and the like;oxycarboxylic acids such as citric acid, tartaric acid, lactic acid,malic acid and the like; carboxylic acids such as formic acid, aceticacid, sorbic acid and the like; aromatic carboxylic acids such assalicylic acid, benzoic acid and the like.

As examples of the preferable inorganic and organic salts, for example,potassium sulfate, sodium sulfate, magnesium sulfate, aluminum sulfate,potassium nitrate, sodium nitrate, magnesium nitrate, aluminum nitrate,calcium nitrate, potassium chloride, magnesium chloride, sodiumchloride, calcium chloride, aluminum chloride, potassium carbonate,sodium carbonate, aluminum carbonate, potassium acetate, sodium acetate,calcium acetate, magnesium acetate, sodium formate, potassium formate,magnesium formate, sodium citrate, sodium tartarate, potassium sorbate,sodium sorbate, sodium salicylate, sodium benzoate and the like aregiven. In particular, potassium sulfate, magnesium sulfate, potassiumchloride, magnesium chloride, aluminum chloride, sodium citrate, sodiumtartarate, potassium sorbate, sodium salicylate and sodium benzoate aremore preferable.

These inorganic or organic salts can be mixed in the form of the salt inthe external agents, or, when the external agent is produced, an acidicor basic material corresponding to the salt in a stoichiometric amountrequired for producing the salt can be added.

In the emulsifying dermatotherapeutic external agents according to thepresent invention, as regards the emulsifier (C), for example, inaddition to the siloxane derivatives, surfactants having an emulsifiersuch as sorbitan fatty acid ester, glycerol fatty acid ester,polyoxyethylene hardened castor oil, isostearylglyceryl ether and thelike can be used. A mixing amount of the emulsifier (C) is preferably0.1 to 30 weight % per all amount of the emulsifying dermatotherapeuticexternal agent of the present invention, and 50 to 100 weight % of thesiloxane derivative (1) is preferably mixed in this emulsifier (C).

In the emulsifying dermatotherapeutic external agent of the presentinvention, further 0 to 40 weight % of other ingredients used for usualdermatotherapeutic external agent can be suitably mixed so far as theydo not lose and reduce the effects of the present invention. As examplesof the other ingredients, for example, powders, humectants,intercellular lipids (ceramides), ultra-violet radiation absorbers,alcohols, chelates, pH regulators, preservatives, thickeners, pigments,perfumes, medicinal effect ingredients and the like can be given.

In these ingredients, by mixing 10 to 40 weight %, preferably 15 to 30weight % of powder in the emulsifying dermatotherapeutic external agentof the present invention a liquefied or creamy foundation can be formed.Regarding the powders, powders generally used for cosmetic preparations,for example, extenders such as talc, mica, kaolin, cericite and thelike; inorganic pigments such as titanium oxide, zinc oxide, iron oxide,ultramarine blue and the like; titanium mica type Pal's pigments;organic pigments or lakes such as blue color #404, red color #202,yellow color #401 and the like can be given. According to the presentinvention, at least one kind of powder can be freely selected for theuse.

As to the emulsifying dermatotherapeutic external agents according tothe present invention, skin cosmetic preparations such as face carecreams or milk lotions, skin care creams or milk lotions, liquefied orcreamy foundations and the like; hair cosmetic preparations; externaldrugs and the like are given.

EXAMPLES

Now, the present invention will be descried in detail with reference tothe exemplary embodiments, and it should be understood that theseembodiments are given for only illustration of the invention and are notintended to be limitative therefor.

EXAMPLE 1

(1) Into a 100 ml two-necked or Claisen flask provided with a condenserand a magnetic stirrer, 97 g (0.72 mol) of 1,1,3,3-tetramethyldisiloxaneand 30 g (0.36 mol) of 1-hexane were put, and 0.72 g (7.2 mmol) of 5%isopropyl alcohol solution of platinic chloride was added to the mixturesolution to stir for 16 hours in an iced water bath. The solution wasdistilled to obtain 52.8 g of transparent colorless liquid (bp: 55° to61° C./4 Torr) in a 67% yield. The obtained product was analyzed by IRand NMR spectra to confirm 1-hexyl-1,1,3,3-tetramethyldisiloxane.

(2) Into a 100 ml two-necked flask provided with a condenser and amagnetic stirrer, 15 g (69 mmol) of1-hexyl-1,1,3,3-tetramethyldisiloxane obtained in (1), 12 g (91 mmol) ofallylglyceryl ether, 1.8 g (1.8 mmol) of 19% ethanol solution ofpotassium acetate and 24 g of isopropyl alcohol were put, and 0.18 g(0.017 mmol) of 5% isopropyl alcohol solution of platinic chloride wasadded to the mixture solution to stir for 17 hours at 40° C. Afterremoving the solvent of the solution by distillation, the reactionproduct was refined by a silica gel column to obtain 22 g of transparentcolorless liquid in a 93% yield. The obtained product was analyzed by IRand NMR spectra to confirm3-(3-hexyl-1,1,3,3-tetramethyldisiloxanyl)propylglyceryl ether (A). Theresult of the analysis of the compound was as follows. ##STR17##

IR (liquid film, cm⁻¹) 3400 (-OH);

2928 (C--H); 1256 (Si--Me); 1064, 842, 796 (Si--O--Si).

¹ H-NMR (δ ppm. in CDCl₃, CHCl₃ standard (7.28 ppm)):

0.04, 0.06 (s, 12H) Si--CH₃ ;

0.08-1.02 (t, 3H) --CH₃ ;

1.14-1.46 (br, 8H) --CH₂ --;

0.40-0.66 (m, 4H) Si--CH₂ --;

1.48-1.72 (m, 2H) CH₂ --CH₂ --O;

3.32-3.59 (m, 4H) CH₂ --O;

3.79-3.98 (m, 1H) CH--OH;

3.59-3.79 (m, 2H) CH--OH;

2.83-2.93 (d, 1H) CH--OH,

2.46-2.59 (dd, 1H) CH₂ --OH.

¹³ C-NMR (δ ppm. in CDCl₃, CHCl₃ standard (77.2 ppm)).

0.46, 0.53 Si--CH₃ ;

14.3, 14.4 --CH₃, CH₂ --CH₂ --CH₂ O;

22.8, 23.4, 23.6, 31.8, 33.2 --CH₂ --;

18.5 Si-CH₂ --;

64.4 CH₂ --OH;

70.7 CH--OH;

72.5 CH₂ --CH₂ --O;

74.6 CH--CH₂ --O.

²⁰ Si--NMR (δppm, in CDCl₃, TMS standard (0 ppm))

7.22, 7.89.

EXAMPLE 2

(1) 1-decyl-1,1,3,3-tetramethyldisiloxane was obtained in a 70% yield inthe same manner as Example 1 (1).

(2) 3-(3-decyl-1,1,3,3-tetramethyldisiloxanyl)propylglyceryl ether (B)was obtained in a 93% yield in the same manner as Example 1 (2). Theresult of the analysis of the compound was as follows. ##STR18##

IR (liquid film, cm⁻¹) 3424 (--OH);

2928 (C--H); 1254 (Si--Me); 1066, 840, 796 (Si-O-Si).

hu 1H-NMR (δ ppm, in CDCl₃, CHCl₃ standard (7.28 ppm):

0.04, 0.06 (s, 12H) Si--CH₃ ;

0.80-0.95 (t, 3H) --CH₂ --;

1.15-1.42 (br, 16H) --CH₂ --;

1.48-1.68 (m, 2H) CHCH₂ --O;

3.38-3.53 (m, 4H) CH₂ --O;

0.38-0.57 (m, 4H) Si--CH₂ --;

3.77-3.94 (m, 1H) CH--OH;

3.53-3.77 (m, 2H) CH₂ --OH;

2.25-2.32 (d, 1H) CH--OH;

2.98-3.08 (t, 1H) CH₂ -OH. ##STR19##

²⁰ Si-NMR (δ ppm, in CDCl₃, TMS standard (0 ppm))

7.22, 7.89.

EXAMPLE 3

(1) 1-hexadecyl-1,1,3,3-tetramethyldisiloxane was obtained in a 70%yield in the same manner as Example 1 (1).

(2) 3-(3-hexadecyl-1,1,3,3-tetramethyldisiloxanyl)propylglyceryl ether(C) was obtained in a 93% yield in the same manner as Example 1 (2). Theresult of the analysis of the compound was as follows. ##STR20##

IR (liquid film, cm⁻¹) 3404 (--OH);

2956 (C--H); 1254 (Si--Me); 1064, 840, 796 (Si-O-Si).

¹ H-NMR (δ ppm, in CDCl₃, CHCl₃ standard (7.28 ppm)):

0.04, 0.06 (s, 12H) Si--CH₃ ;

0.81-0.96 (t, 3H) --CH₃ ;

1.16-1.41 (br, 28H) --CH₂ --;

0.41-0.59 (m, 4H) Si--CH₂ --;

1.53-1.70 (m, 2H) CH₂ --CH₂ --O;

3.36-3.59 (m, 4H) CH₂ --O;

3.59-3.80 (m, 2H) CH₂ --OH;

2.83-2.93 (d, 1H) CH--OH;

2.46-2.59 (dd, 1H) CH₂ --OH. ##STR21##

²⁰ Si--NMR (δ ppm, in CDCl₃, TMS standard (0 ppm))

7.22, 7.93.

EXAMPLE 4

Into a 100 ml two-necked flask provided with a condenser and a magneticstirrer, 20 g (30 mmol) of nonadecamethylnonasiloxane, 9.5 g (39 mmol)of 10-undecenylglyceryl ether, 0.77 g (0.78 mmol) of 10% ethanolsolution of potassium acetate and 18.5 g of isopropyl alcohol were put,and 0.20 g (7.7×10⁻³ mmol) of 2% isopropyl alcohol solution of platinicchloride was added to the mixture solution to heat the solution to raiseits temperature. While the solution was kept to 40° C., the solution wasstirred for 3.5 hours. After removing the solvent from the solution bydistillation, the obtained reaction product was dissolved in hexane, andthe solution was filtered. After removing the solvent from the solution,the obtained reaction product was redefined by a silica gel column toobtain 21.7 g of transparent colorless oil in a 80% yield. The obtainedproduct was analyzed by IR and NMR spectra to confirmnonadecamethylnonasiloxanylundecylglyceryl ether result of the analysisof the compound was as follows. ##STR22##

¹ H-NMR (δ ppm, in CDCl₃, CHCl₃ standard (7.28 ppm))

0.00-0.18 (m, 57H) Si--CH₃ ;

0.48-0.64 (m, 2H) Si--CH₂ --;

1.20-1.42 (br, 10H) --CH₂ --;

1.50-1.68 (m, 2H) CH₂ --CH₂ --O;

3.40-3.58 (m, 4H) CH₂ --O;

3.78-3.96 (m, 1H) (m, 1H) CH₂ --OH;

3.58-3.78 (m, 2H) CH₂ --OH;

2.67-2.72 (d, 1H) CH--OH;

2.21-2.35 (dd, 1H) CH₂ --OH; ##STR23##

EXAMPLE 5

Pentamethyldisiloxanylundecylglyceryl ether (E) was obtained in a 56%yield in the same manner as Example 4. The result of the analysis of thecompound was as follows. ##STR24##

IR (liquid film, cm⁻¹) 3394 (--OH)

2926, 2860 (C--H); 1254 (Si--Me); 1062, 843 (Si--O--Si).

¹ H-NMR (δ ppm, in CDCl₃, CHCl₃ standard (7.28 ppm));

0.05, 0.07 (s, 15H) Si--CH₃ ;

0.43-0.62 (m, 2H) Si--CH₂ --;

1.14-1.40 (br, 16H) --CH₂ --;

1.50-1.68 (m, 2H) CH₃ --CH₂ --O;

3.38-3.58 (m, 4H) CH₂ --O;

3.80-3.95 (m, 1H) CH--OH;

3.58-3.80 (m, 2H) CH₂ --OH;

2.72-2.81 (d, 1H) CH--OH;

2.31-2.47 (br, 1H) CH₂ --OH.

¹³ C-NMR (δ ppm, in CDCl₃, CHCl₃ standard (77.2 ppm)):

0.51, 2.14 Si--CH₃ ;

18.6 Si--CH₃ --;

23.4, 26.3, 29.6, 33.6 --CH₂ --;

64.4 CH₂ --OH;

70.7 CH--OH;

72.0 CH--CH₂ --O;

72.6 CH₂ --CH₂ --O.

²⁰ Si--NMR (δ ppm, in CDCl₂, TMS standard (0 ppm))

6.97, 7.61.

EXAMPLE 6

Undecamethylpentasiloxanylundecylglyceryl ether (F) was obtained in a48% yield in the same manner as Example 4. At this time, since1,5-dihydrodecamethylpentasiloxane was included in a raw material ofundecamethylpentasiloxane,1,5-bis[11-(2,3-dihydroxypropoxy)undecyl]decamethylpentasiloxane (C) wasobtained at the same time. The obtained compound (G) was isolated andrefined by a silica gel column. The structures of the obtained productswere confirmed by an analysis using IR and NMR spectra. The result ofthe analysis of the compounds was as follows. ##STR25##

IR (liquid film, cm⁻¹) 346 (--OH);

2962, 2926, 2860 (C--H); 1260 (Si--Me); 1035, 801 (Si--O--Si).

¹ H-NMR (δ ppm, in CDCl₃, CHCl₃ standard (7.28 ppm)):

-0.02-0.18 (s, 33H) Si--CH₃ ;

0.46-0.63 (m, 2H) Si--CH₂ --;

1.17-1.42 (br, 16H) --CH₂ --;

1.48-1.70 (m, 2H) CH₂ --CH₂ --O;

3.38-3.59 (m, 4H) CH₂ --O;

3.77-3.97 (m, 1H) CH--OH;

3.59-3.77 (m, 2H) CH₂ --H;

2.83-2.98 (d, 1H) CH--OH;

2.46-2.64 (br, 1H) CH₂ --OH. ##STR26##

²⁰ Si-NMR (δ ppm, in CDCl₃, TMS standard (0 ppm)):

7.28, 7.61, a, e;

-21.4, -21.7, -22.2, b, c, d. ##STR27##

IR (liquid film, cm⁻¹) 3404 (-OH);

2924, 2856 (C--H); 1260 (Si--Me); 1080, 1034, 802 (Si--O--Si);

¹ H-NMR (δ ppm, in CDCl₃, CHCl₃ standard (7.28 ppm));

0.03. 0.05 (s, 30H) Si--CH₃ ;

0.54 (t, 4H) Si--CH₂ --;

1.28 (br, 32H) --CH--;

1.48-1.69 (m, 4H) CH₂ --CH₂ --O;

2.92 (t, 2H) CH₂ --OH;

3.20 (d, 2H) CH--OH;

3.36-3.57 (m, 8H) CH₂ --O;

3.57-3.78 (m, 4H) CH₂ --OH;

3.78-3.96 (m, 2H) CH--OH. ##STR28##

²⁰ Si-NMR (δ ppm, in CDCl₃, TMS standard (0 ppm)):

-22.3, C;

-21.7, B;

78.62, A.

EXAMPLE 7

Into a 100 ml two-necked flask provided with a condenser and a magneticstirrer, 30 g (18.5 mmol) of α,ω-dihydromethylpolysiloxane (averagechain length of 20), 11.8 g (48.3 mmol) of 10-undecenylglyceryl ether,0.95 g (0.97 mmol) of 10% ethanol solution of potassium acetate and 24 gof isopropyl alcohol were put, and 0.26 g (0.010 mmol) of 2% isopropylalcohol solution of platinic chloride was added to the mixture solutionto heat the solution to raise its temperature. While the solution waskept to 50° C. the solution was stirred for 2 hours. After removing thesolvent from the solution by distillation, unreacted10-undecenylglyceryl ether was removed by vacuum distillation to obtaina brown high viscous material. This brown high viscous material wastreated by active carbon to obtain 35.0 g of transparent colorless highviscous material in a 89.7% yield.

The obtained product was analyzed by IR and NMR spectra to confirmα,ω-bis[11-(2,3-dihydroxypropoxy)undecyl]dimethylpolysiloxane (averagechain length of 20) (H). The result of the analysis of the compound wasas follows. ##STR29##

IR (liquid film, cm⁻¹) 3420 (--OH);

2964, 2928, 2860 (C--H); 1262 (Si--Me); 1100, 1026, 802 Si--O--Si).

¹ H-NMR (δ ppm, in CDCl₃, CHCl₃ standard (7.28 ppm)):

0.00 (br, approx. 132H) Si--CH₃ ;

0.57 (t, 4H) Si--CH₂ --;

1.39 (br, 32H) --CH₂ --;

1.47-1.70 (m, 4H) CH_(2l) --CH₂ --O;

2.22 (br, 2H) CH₂ --OH;

2.62 (br, 2H) CH--OH;

3.30-3.59 (m, 8H) CH₂ --O;

3.59-3.80 (m, 4H) CH₂ --OH;

3.80-3.96 (m, 2H) CH--OH.

¹³ C-NMR (δ ppm, in CDCl₃, CHCl₃ standard (77.2 ppm)):

0.39, 1.23, 1.36 Si--CH₃ ;

18.5 Si--CH₂ --;

23.4, 26.3, 29.6, 29.8, 33.7 --CH₂ --;

64.7 CH₂ --OH;

70.6 CH--OH;

72.0 CH₂ --CH₂ --O;

72.7 CH--CH₂ --O. ##STR30##

EXAMPLE 8

α,ω-bis[11-(2,3-dihydroxypropoxy)undecyl]dimethylpolysiloxane (averagechain length of 50) (I) in a 95.3% yield in the same manner as Example7. The result of the analysis of the compound was as follows. ##STR31##

IR (liquid film, cm⁻¹) 3420 (--OH);

2968, 2932 (C--H); 1264 (Si--Me); 1094, 1020, 866, 802 (Si--O--Si).

¹ H-NMR (δ ppm, in CDCl₃, CHCl₃ standard (7.28 ppm)):

0.08 (br, approx. 312H) Si--CH₃ ;

0.57 (t, 4H) Si--CH₂ --;

1.30 (br, 32H) --CH₂ --;

1.48-1.80 (m, 4H) CH₂ --CH₂ --O;

2.20 (br, 2H) CH₂ --OH;

2.63 (br, 2H) CH--OH;

3.38-3.60 (m, 8H) CH₂ --O;

3.60-3.81 (m, 4H) CH₂ --OH;

3.81-3.97 (m, 2H) CH--OH.

¹³ C-NMR (δ ppm, CDCl₃, CHCl₃ standard (77.2 ppm));

0.38, 1.22, 1.36, 1.96 Si--CH₃ ;

18.5 Si--CH₂ --;

23.4, 26.3, 29.6, 29.8. 33.7 --CH₂ --;

64.7 CH₂ --OH;

70.8 CH--OH;

72.1 CH₂ --CH₂ --O;

72.7 CH--CH₂ --O. ##STR32##

EXAMPLE 9

(1) Into a 100 ml two-necked flask provided with a condenser and amagnetic stirrer, 32.8 g (56.6 mmol) ofα,ω-dihydrohexadecamethyldisiloxane and 4.0 g (28.5 mmol) of 1-decenewere put, and 3.0 mg (5.8×10⁻³ mmol) of platinic chloride was added tothe mixture solution to stir for 6 hours in a water bath. The solutionwas distilled to obtain 11.0 g of transparent colorless liquid (bp: 160°C./0.005 Torr) in a 54% yield. The obtained product was analyzed by IRand NMR spectra to confirm 1-decyl-15-hydrohexadecamethyloctasiloxane.

(2) Into a 100 ml two-necked flask provided with a condenser and amagnetic stirrer, 10 g (13.9 mmol) of1-decyl-15-hydrohexadecamethyloctasiloxane obtained in (1) , 4.4 g (18.0mmol) of 10-undecenylglyceryl ether. 0.35 g (0.36 mmol) of 10% ethanolsolution of potassium acetate and 10 g of isopropyl alcohol were put,and 0.093 g (3.6×10⁻³ mmol) of 2% isopropyl alcohol solution of platinicchloride was added to the mixture solution to heat the solution to raiseits temperature. While the solution was kept to 40° C. the solution wasstirred for 3 hours. After removing the solvent from the solution bydistillation, the reaction product was refined by a silica gel column toobtain 11.8 g of transparent colorless oil in a 88% yield. The obtainedproduct was analyzed by IR and NMR spectra to confirm15-decylhexadecamethyloctasiloxanylundecylglyceryl ether (J). The resultof the analysis of the compound was as follows. ##STR33##

IR (liquid film, cm⁻¹) 3400 (--OH);

2964, 2928, 2860 (C--H); 1262 (Si--Me); 1096, 1026, 840, 804(Si--O--Si).

¹ H-NMR (δ ppm, in CDCl₃, CHCl₃ standard (7.28 ppm)):

-0.02-0.10 (m, 48H) Si--CH₃ ;

0.50 (t, 4H) Si--CH₂ --;

0.87 (t, 3H) --CH₃ ;

1.24 (br, 32H) --CH₂ --;

1.47-1.66 (m, 2H) CH_(2l) --CH₂ --O;

2.32 (t, 1H) CH₂ --OH;

2.71 (d, 1H) CH--OH;

3.36-3.57 (m, 4H) CH₂ --O;

3.57-3.78 (m, 2H) CH₂ --OH;

3.73-3.90 (m, 1H) CH--OH. ##STR34##

EXAMPLE 10

Into a 100 ml two-necked flask provided with a condenser and a magneticstirrer, 15 g (4.4 mmol) of organohydrogen siloxane represented by thefollowing formula (K'). ##STR35## 8.1 g (33 mmol) of10-undecenylglyceryl ether, 0.65 g (0.66 mmol) of 10% ethanol solutionof potassium acetate and 50 g of isopropyl alcohol were put, and 0.17 g(6.6×10⁻³ mmol) of 2% isopropyl alcohol solution of platinic chloridewas added to the mixture solution to heat the solution to raise itstemperature. While the solution was kept to 40° C. the solution wasstirred for 2.5 hours. After removing the solvent from the solution bydistillation, the solid was treated by active carbon, and unreacted10-undecenylglyceryl ether was removed by vacuum distillation to obtaina brown high viscous material. The obtained product was analyzed by IRand NMR spectra to confirm a compound represented by the followingformula (K). The result of the analysis of the compound was as follows.##STR36##

IR (liquid film cm⁻¹) 3400 (--OH);

2968, 2932, 2860 (C--H); 1262 (Si--Me); 1096, 1022, 844 (Si--O--Si).

¹ H-NMR (δ ppm, in CDCl₃, CHCl₃ standard (7.28 ppm)).

0.01 (s, approx. 273H) Si--CH₃ ;

0.38-0.58 (m, 10H) Si--CH₂ --;

1.10-1.41 (br, 80H) --CH₂ --;

1.44-1.86 (m, 10H) CH₂ --CH₂ --O;

3.30-3.55 (m, 20H) CH₂ --O;

3.55-3.77 (m, 10H) CH₂ --OH;

3.77-3.90 (m, 5H) CH--OH.

EXAMPLE 11

A compound represented by the following formula (L) was obtained in a97% yield in the same manner as Example 10. The result of the analysisof the compound was as follows. ##STR37##

IR (liquid film, cm⁻¹). 3420 (--H);

2968, 2932, 2860 (C--H); 1264 (Si--Me); 1096, 1026, 802 (Si--O--Si).

¹ H-NMR (δ ppm, in CDCl_(3l) , CHCl₃ standard (7.28 ppm)):

0.00 (s, approx. 390H) Si--CH₃ ;

0.35-0.50 (m, 8H) Si--CH₂ --;

1.08-1.39 (br, 64H) --CH₂ --;

1.39-1.62 (br, 8H) CH₂ --CH₂ --O;

1.96-2.29 (br, 4H) CH₂ --OH;

2.43-2.68 (br, 4H) CH--OH;

3.38-3.50 (m, 16H) CH₂ --O;

3.50-3.70 (m, 8H) CH_(2l) --OH;

3.70-3.86 (m, 4H) CH--OH.

EXAMPLE 12

A compound represented by the following formula (M) was obtained in a99% yield in the same manner as Example 10. The result of the analysisof the compound was as follows. ##STR38##

IR (liquid film, cm⁻¹) 3424 (--OH);

2964, 2928, 2860 (C--H); 1262 (Si--Me); 1096, 1034, 864, 798(Si--O--Si).

¹ H-NMR (δ ppm, in CDCl₃, CHCl₃ standard (7.28 ppm)):

0.00 (s. approx. 510H) Si--CH₃ ;

0.34-0.55 (m, 8H) Si--CH₂ --;

1.02-1.38 (br, 64H) --CH₂ --;

1.38-1.66 (br, 8H) CH₂ --CH₂ --O;

1.98-2.40 (br, 4H) CH₂ --OH;

2.40-2.78 (br, 4H) CH--OH;

3.26-3.53 (m, 16H) CH₂ --O;

3.53-3.70 (m, 8H) CH₂ --OH;

3.70-3.88 (m, 4H) CH--OH.

EXAMPLE 13

Into a 100 ml two-necked flask provided with a condenser and a magneticstirrer, 10 g, (7.5 mmol) of organohydrogen siloxane represented by thefollowing formula (N') ##STR39## and 8.4 g (60.2 mmol) of decene wereput, and 8.3×10⁻³ ml of 2% isopropyl alcohol solution of platinicchloride was added to the mixture solution to heat the solution to 40°C. After 20 minutes. 20 g of isopropyl alcohol, 4.6 g (35 mmol) ofallylglyceryl ether, 0.44 g of 10% ethanol solution of potassium acetateand 0.12 ml of 2% isopropyl alcohol solution of platinic chloride wereadded to the solution to heat to 40° C. After 2 hours, the isopropylalcohol was removed by distillation. After the solution was treated byactive carbon, and uncreated allylglyceryl ether was removed by vacuumdistillation to obtain 22 g of colorless viscous material. The obtainedproduct was analyzed by IR and NMR spectra to confirm a compoundrepresented by the following formula (N). The result of the analysis ofthe compound was as follows. ##STR40##

IR (liquid film, cm⁻¹) 3400 (--OH);

2965, 2925, 2860 (C--H); 805, 850, 1260 (Si--Me); 1090, 1030(Si--O--Si).

¹ H-NMR (δ ppm, in CDCl₃, CHCl₃ standard (7.28 ppm));

0.06-0.11 (bs, 90H) Si--CH₃ ;

0.51 (m, 24H) Si--CH₂ --CH₂ --;

0.90 (t, 24H) --CH₂ --CH₃ ;

1.28 (br, 136H) --CH₂ --;

1.64-1.68 (br, 8H) --OH;

3.44-3.87 (m, 28H) ##STR41##

EXAMPLE 14

22 g of compound represented by the following formula (O) was obtainedin the same manner as Example 13 except that 11.7 g (83 mmol) of deceneand 1.1 g (8.3 mmol) of allylglyceryl ether were used. The result of theanalysis of the compound was as follows. ##STR42##

IR (liquid film, cm⁻¹) 3425 (--OH),

2970, 2930, 2865 (C--H); 805, 845, 1260 (Si--Me); 1095, 1025(Si--O--Si).

¹ H-NMR (δ ppm, in CDCl₃, CHCl₃ standard (7.28 ppm)):

0.06-0.12 (bs, 90H) Si--CH₃ ;

0.50 (m, 24H) Si--CH₂ --CH₂ --;

0.90 (t, 33.2H) --CH₂ --CH₃ ;

1.28 (br, 179.1H) --CH₂ --;

1.62-1.67 (br, 1.8H) --OH;

3.45-3.88 (m, 6.5H) ##STR43##

EXAMPLE 16

Creamy transparent or semitransparent emulsified compositions

Emulsified compositions having compositions shown in Table 4 wereprepared, and appearance and emulsification stability of each emulsifiedcomposition were evaluated right after preparation thereof, as shown inTable 4.

Preparation method

First, ingredients (1) to (3) were mixed, and then, while stirring themixture by an emulsifying apparatus, previously mixed ingredients (4) to(8) were gradually added to the mixture to carry out the emulsificationto obtain emulsified compositions.

Emulsification stability evaluation method

The obtained emulsified compositions were preserved at 25° C. and theirappearance was observed after one month to evaluate the emulsificationstability according to the following standard.

O: there is no change in state,good

Δ: there is slight separation and/or aggregation

X: there is separation and/or aggregation, insufficient emulsification

                                      TABLE 4                                     __________________________________________________________________________                                      (wt %)                                               Inventive composition                                                Components                                                                             1    2    3    4    5    6                                           __________________________________________________________________________    (1) Siloxane                                                                            2    2    2   2     2    2                                          derivative (L)                                                                (2) Dimethyl                                                                  polysiloxane                                                                  polyoxyalkylene                                                               copolymer*                                                                    (3) Dimethyl                                                                           23   23   23   38   23   23                                          polysiloxane                                                                  (50 cs)                                                                       (4) Glycerol                                                                           30   39   48   30.8                                                  (5) 1.3                      39                                               Butylene glycol                                                               (6) Sorbitol                      39                                          (7) Magnesium                                                                           1    1    1   1     1    1                                          sulfate                                                                       (8) Purified                                                                           44   35   26   28.2 35   35                                          water                                                                         Appearance                                                                             Semi-                                                                              Trans                                                                              Semi-                                                                              Trans-                                                                             Trans-                                                                             Trans-                                               trans-                                                                             parence                                                                            trans-                                                                             parence                                                                            parence                                                                            parence                                              parence   parence                                                    Emulsion ◯                                                                      ◯                                                                      ◯                                                                      ◯                                                                      ◯                                                                      ◯                               stability                                                                     __________________________________________________________________________             Comparative composition                                              Components                                                                             1    2    3    4    5    6                                           __________________________________________________________________________    (1) Siloxane                                                                  derivative (L)                                                                (2) Dimethyl                                                                            2    2    2   2     2    2                                          polysiloxane                                                                  polyoxyalkylene                                                               copolymer*                                                                    (3) Dimethyl                                                                           23   23   23   38   23   23                                          polysiloxane                                                                  (50 cs)                                                                       (4) Glycerol                                                                           30   39   48   30.8                                                  (5) 1.3                      39                                               Butylene glycol                                                               (6) Sorbitol                      39                                          (7) Magnesium                                                                           1    1    1   1     1    1                                          sulfate                                                                       (8) Purified                                                                           44   35   26   28.2 35   35                                          water                                                                         Appearance                                                                             Semi-                                                                              Trans                                                                              Semi-                                                                              Trans-                                                                             Trans-                                                                             Trans-                                               trans-                                                                             parence                                                                            trans-                                                                             parence                                                                            parence                                                                            parence                                              parence   parence                                                    Emulsion Δ                                                                            X    X    X    X    X                                           stability                                                                     __________________________________________________________________________     *Toray Silicone SH3775C (manufactured by Toray Silicone Co.))            

As apparent from Table 4, the emulsified compositions of the presentinvention exhibited extremely excellent emulsification states. However,in the comparative compositions, an oil phase separation to an upperlayer occurred with the passage of time and the comparative compositionsare inferior in stability.

Further, emulsified compositions prepared by using another siloxanederivative (D), (F), (H), (I), (J), (K) or (M) in place of the siloxanederivative (L) used in the present compositions 1 to 6 in Table 4 alsoexhibit superior stability than the comparative compositions.

EXAMPLE 17

Creamy emulsified compositions.

Emulsified compositions having compositions shown in Table 5 wereprepared, and emulsification stability of each emulsified compositionwas evaluated, as shown in Table 5.

Preparation method

First, ingredients (1) to (3) were mixed, and then, while stirring themixture by an emulsifying apparatus, previously mixed ingredients (4) to(6) were gradually added to the mixture to carry out the emulsificationto obtain emulsified compositions.

                  TABLE 5                                                         ______________________________________                                                                (wt %)                                                              Composition of the                                                                        Comparative                                                       Invention   composition                                         Components      7        8        7    8                                      ______________________________________                                        (1) Siloxane derivative (M)                                                                    2        2                                                   (2) Dimethyl polysiloxane          2    2                                     polyoxyalkelene copolymer*                                                    (3) Dimethyl polysiloxane                                                                     23       23       23   23                                     (50 cs)                                                                       (4) Glycerol    64       23       64   23                                     (5) Magnesium sulfate                                                                          1        1        1    1                                     (6) Purified water                                                                            10       51       10   51                                     Emulsion stability                                                                            ◯                                                                          ◯                                                                          X    X                                      ______________________________________                                         *Silicone X22-4013 (manufactured by Sinetsu Co.)                         

Emulsification stability evaluation method

The obtained emulsified compositions were evaluated in the same manneras Example 16.

As apparent from Table 5, the emulsified compositions of the presentinvention exhibited extremely excellent emulsification states. However,in the comparative compositions, an oil phase separation to an upperlayer occurred with the passage of time and their stability wasinferior.

Further, emulsified compositions prepared by using another siloxanederivative (D), (F), (H), (I), (J), (K) or (L) in place of the siloxanederivative (M) used in the present compositions 7 and 8 in Table 5 alsoexhibit superior stability than the comparative compositions.

EXAMPLE 18

    ______________________________________                                        Hand cream:                                                                   (Compositions)       (weight %)                                               ______________________________________                                        (1) siloxane derivative (L)                                                                        2.0                                                      (2) methylphenylpolysiloxane                                                                       5.0                                                      (3) decamethylcyclopentasiloxane                                                                   5.0                                                      (4) dimethylpolysiloxane (50 cs)                                                                   10.0                                                     (5) pefume           0.2                                                      (6) glycerol         20.0                                                     (7) 1,3-butylene glycol                                                                            15.0                                                     (8) magnesium sulfate                                                                              1.0                                                      (9) purified water   41.8                                                     ______________________________________                                    

Preparation

First, ingredients (1) to (5) were mixed, and then, while stirring themixture by an emulsifying apparatus, previously mixed ingredients (6) to(9) were gradually added to the mixture to carry out the emulsificationto obtain a hand cream.

EXAMPLE 19

    ______________________________________                                        Wet-holding cream:                                                            (Compositions)        (weight %)                                              ______________________________________                                         (1) dimethylpolysiloxane (50 cs)                                                                   10.0                                                     (2) decamethylcyclopentasiloxane                                                                   5.0                                                      (3) squalene         8.0                                                      (4) siloxane derivative (I)                                                                        2.0                                                      (5) isostearylglyceryl ether                                                                       1.0                                                      (6) glycerol         20.0                                                     (7) 1,3-butylene glycol                                                                            5.0                                                      (8) sorbitol         5.0                                                      (9) magnesium sulfate                                                                              1.0                                                     (10) perfume          0.2                                                     (11) purified water   41.8                                                    ______________________________________                                    

Preparation

First, ingredients (1) to (5) and (10) were mixed, and then, whilestirring the mixture by an emulsifying apparatus, previously mixedingredients (6) to (9) and (11) were gradually added to the mixture tocarry out the emulsification to obtain a wet-holding cream.

EXAMPLE 20

    ______________________________________                                        Creamy foundation:                                                            (Compositions)            (weight %)                                          ______________________________________                                        (1) siloxane derivative (L)                                                                             2.0                                                 (2) dimethylpolysiloxane (50 cs)                                                                        10.0                                                (3) octamethylcyclotetrasiloxane                                                                        8.0                                                 (4) perfume               0.2                                                 (5) silicone-treated cosmetic preparation powder*)                                                      15.0                                                (6) glycerol              30.0                                                (7) magnesium sulfate     1.0                                                 (8) purified water        33.8                                                ______________________________________                                         *)the cosmetic preparation powder having the following composition was        used as raw powder material. Before using this cosmetic preparation           powder, the powder was added by 2% methylhydorogen polysiloxane {KF99         (Trade Name) manufactured by Shinetsu Silicone Co., Ltd.}, and the mixtur     was heattreated.                                                         

    cosmetic preparation powder composition:                                      (1) titanium oxide  8 (parts by weight)                                       (2) talc            4                                                         (3) red iron oxide  1.2                                                       (4) yellow iron oxide                                                                             2.6                                                       (5) black iron oxide                                                                              0.2                                                       ______________________________________                                    

Preparation

First, ingredients (1) to (4) were mixed, and then after addingingredient (5) in the mixture to disperse therein, while stirring themixture by an emulsifying apparatus, previously mixed ingredients (6) to(8) were gradually added to the mixture to carry out the emulsificationto obtain a creamy foundation.

EXAMPLE 21

    ______________________________________                                        Suntan cream:                                                                 (Compositions)        (weight %)                                              ______________________________________                                         (1) siloxane derivative (J)                                                                        5.0                                                      (2) dimethylpolysiloxane (50 cs)                                                                   15.0                                                     (3) methylphenylpolysiloxane                                                                       5.0                                                      (4) p-dimethylaminobenzoic acid**)                                                                 5.0                                                      (5) oxybenzone       0.5                                                      (6) perfume          0.2                                                      (7) glycerol         8.0                                                      (8) 1,3-butylene glycol                                                                            15.0                                                     (9) glucose          2.0                                                     (10) sodium chloride  1.0                                                     (11) purified water   balance                                                 ______________________________________                                         **)Escalol 507 (Trade Name) (manufactured by Van Dike Co., Ltd.)         

Preparation

First, ingredients (1) to (6) were mixed, and then, while stirring themixture by an emulsifying apparatus, previously mixed ingredients (7) to(11) were gradually added to the mixture to carry out the emulsificationto obtain a suntan cream.

The emulsified cosmetic preparations of Examples 18 to 21 were allstable and extremely superior in wet-holding property, usage feeling orthe like.

EXAMPLE 22

Emulsification stabilizing effect

Cosmetic preparation bases are prepared from the following compositionsincluding siloxane derivative (N) or (G) or conventional emulsifiers ascompounds to be examined, and their emulsification stability are tested,as shown in Table 8.

    ______________________________________                                        Compositions:                                                                 ______________________________________                                        (1) liquid paraffin   5 (parts by weight)                                     (2) purified water   94                                                       (3) magnesium sulfate                                                                               0.2                                                     (4) compound to be examined                                                                         0.8                                                     ______________________________________                                    

Preparation of cosmetic preparation bases

To 5 parts by weight of liquid paraffin, 1 part by weight of sum ofmagnesium sulfate and a compound to be examined were added, and theywere mixed and heated to 70° C. To this mixture, 94 parts by weight ofion-exchanged or purified water previously heated to 70° C. wasgradually added to carry out emulsification. After emulsification, whilethe mixture was stirred, the mixture was air-cooled to a roomtemperature to obtain a cosmetic preparation base.

                                      TABLE 6                                     __________________________________________________________________________                                         State (after 7 days)                                           Emulsion                                                                           State     Demulsification                                                                       Demulsification                  Test composition      type (right after)                                                                           of Oil phase                                                                          of Aqueous                       __________________________________________________________________________                                                 phase                            Compound of                                                                          Siloxane derivative (N)                                                                      W/O  Uniform cream                                                                           0       0                                the Invention                                                                        Siloxane derivative (G)                                                                      W/O  Uniform cream                                                                           0       0                                Comparative                                                                          α-monooleyl glyceryl ether                                                             W/O  Slightly uniform                                                                        90      70                               composition                cream                                                     α-monostearyl glycery ether                                                            W/O  Slightly ununiform                                                                      100     85                                                          cream                                                     2-hexadecyl-eicosyl                                                                          --   Separation                                                                              100     100                                     α-monoglyceryl ether                                                    Sorbitan monooleate                                                                          W/O  Slightly ununiform                                                                      54      81                                                          cream                                                     Sorbitan sesquioleate                                                                        W/O  Slightly uniform                                                                        21      36                                                          cream                                                     Sorbitan monostearate                                                                        W/O  Ununiform cream                                                                         90      100                                     Glycerol monooleate                                                                          W/O  Slightly ununiform                                                                      15      32                                                          cream                                                     Glycerol monostearate                                                                        W/O  Ununiform cream                                                                         100     100                                     Polyoxyethylene(5) oleyl ether                                                               O/W  Uniform cream                                                                           0       15                                      Polyoxyethylene(7) sorbitol                                                                  W/O  Slightly ununiform                                                                      26      79                                      tetraoleate         cream                                                     Polyoxyethylene(20) sorbitan                                                                 O/W  Slightly ununiform                                                                      0       15                                      monostearate        cream                                                     Polyoxyethylene(5) sesqui-                                                                   O/W  Slightly ununiform                                                                      0       21                                      lauryl phosphate    cream                                                     Sodium stearyl sulfate                                                                       O/W  Slightly ununiform                                                                      0       85                                                          cream                                              __________________________________________________________________________     ##EQU1##

As apparent from the above-described results, from the compositionsmixing with compounds of the present invention, water-in-oil typecosmetic preparation bases readily blending a lot of water could beobtained, and their emulsification stability was excellent. On the otherhand, when the conventional emulsifiers were used, it was difficult toobtain water-in-oil type cosmetic preparation bases. Even whenwater-in-oil type cosmetic preparation bases could be produced, an oilor water component was separated, and no stable emulsified base could beobtained.

EXAMPLE 23

Cosmetic preparation bases are prepared from the following compositionsincluding siloxane derivative (N) or (G) or conventional emulsifiers ascompounds to be examined in the same manner as Example 22, and theiremulsification stability are tested, as shown in Table 7.

                                      TABLE 7                                     __________________________________________________________________________                               Emulsion                                                                           State                                         Test composition           type (after 5 days)                                __________________________________________________________________________    Composition of                                                                        Siloxane derivative (N)                                                                          W/O  Excellent                                     the Invention                                                                         Siloxane derivative (G)                                                                          W/O  Excellent                                     Comparative                                                                           α-Mono-isostearyl glyceryl ether                                                           W/O  Separation of Oil phase (13%)                 composition                                                                           Dimethyl polysiloxane polyoxy-                                                                   W/O  Separation of Oil phase (40%)                         alkylene copolymer (Toray SH3775C)                                            Glycerol monostearate                                                                            W/O  Separation of Oil phase                       __________________________________________________________________________                                    (100%)                                    

    ______________________________________                                        Compositions:                                                                 ______________________________________                                        (1) liquid paraffin  12.0 (parts by weight)                                   (2) dimethylpolysiloxane (50 cs)                                                                   11.0                                                     (3) magnesium sulfate                                                                               1.0                                                     (4) compound to be examined                                                                         2.0                                                     (5) purified water   74.0                                                     ______________________________________                                    

As apparent from the above-described results, in case that the compoundsof the present invention were used, even when a silicone was included inan oil phase, cosmetic preparation bases having excellent emulsificationstability could be obtained.

EXAMPLE 24

    ______________________________________                                        Nourishing cream:                                                             (Compositions)       (weight %)                                               ______________________________________                                         (1) siloxane derivative (O)                                                                       2.0                                                       (2) potassium sulfate                                                                             0.5                                                       (3) squalane        4.0                                                       (4) liquid paraffin 2.0                                                       (5) hexadecyl-2-ethylhexanoate                                                                    2.0                                                       (6) potassium benzoate                                                                            0.3                                                       (7) propylene glycol                                                                              2.0                                                       (8) acetic acid dl-α-tocopherol                                                             0.1                                                       (9) perfume         0.1                                                      (10) purified water  balance                                                  ______________________________________                                    

Preparation

First, ingredients (1) to (5) were mixed and heated to 75° C., and then,while stirring the mixture, previously mixed ingredients (6), (7) and(10) previously heated to 70° C. were gradually added to the mixture tocarry out the emulsification. After the emulsification, the mixture wascooled to 60° C. and ingredients (8) and (9) were added to the mixture.Further, the mixture was air-cooled to a room temperature to obtain anourishing cream.

The obtained nourishing cream was excellent in emulsification stability,and its usage feeling was also excellent.

Other nourishing creams obtained by mixing 0.5% of potassium chloride,magnesium chloride or magnesium nitrate in place of the potassiumsulfate in the same manner as described above exhibited the sameresults.

EXAMPLE 25

    ______________________________________                                        Hand cream:                                                                   (Compositions)       (weight %)                                               ______________________________________                                        (1) siloxane derivative (B)                                                                        1.5                                                      (2) aluminum chloride                                                                              0.8                                                      (3) IPM (isopropyl myristate)                                                                      4.5                                                      (4) dimethylpolysiloxane (50 cs)                                                                   4.0                                                      (5) methyl p-oxybenzoate                                                                           0.2                                                      (6) sorbitol         10.0                                                     (7) purified water   balance                                                  ______________________________________                                    

Preparation

First, ingredients (1) to (4) were mixed and heated to 75° C. and then,while stirring the mixture, previously mixed ingredients (5) to (7)previously heated to 75° C. were gradually added to the mixture to carryout the emulsification. Then, the mixture was air-cooled to a roomtemperature to obtain a hand cream.

The obtained hand cream was excellent in emulsification stability for along period of time, and its usage feeling was also excellent. Also, thehand cream possesses water repellency and exhibited superior properties.

EXAMPLE 26

    ______________________________________                                        Cold cream (water-in-oil type):                                               (Compositions)     (weight %)                                                 ______________________________________                                        (1) siloxane derivative (N)                                                                      5.5                                                        (2) sodium nitrate 1.0                                                        (3) liquid paraffin                                                                              10.0                                                       (4) oleyl alcohol  1.0                                                        (5) potassium sorbate                                                                            0.2                                                        (6) glycerol       5.0                                                        (7) perfume        0.1                                                        (8) purified water balance                                                    ______________________________________                                    

Preparation

First, ingredients (1) to (4) were mixed and heated to 75° C., and then,while stirring the mixture, previously mixed ingredients (5), (6) and(8) previously heated to 75° C. were gradually added to the mixture tocarry out the emulsification. After cooling the mixture, an ingredient(7) was added to the mixture to obtain a cold cream.

The obtained cold cream exhibited excellent emulsification stability.

EXAMPLE 27

    ______________________________________                                        Vanishing cream (water-in-oil type):                                          (Compositions)       (weight %)                                               ______________________________________                                        (1) siloxane derivative (C)                                                                        2.0                                                      (2) aluminum monostearate                                                                          0.2                                                      (3) calcium chloride 0.4                                                      (4) stearic acid     1.0                                                      (5) glycerol tri-2-ethylhexanoate                                                                  7.0                                                      (6) propyl p-oxybenzoate                                                                           0.2                                                      (7) sorbitol         5.0                                                      (8) perfume          0.2                                                      (9) purified water   balance                                                  ______________________________________                                    

Preparation

First, ingredients (1) to (6) were mixed and heated to 75° C. and then,while stirring the mixture, previously mixed ingredients (7) and (9)previously heated to 75° C. were gradually added to the mixture to carryout the emulsification. After cooling the mixture, an ingredient (8) wasadded to the mixture to obtain a vanishing cream.

The obtained vanishing cream was excellent in emulsification stabilityfor a long period of time, and its usage feeling was also excellent.

EXAMPLE 28

    ______________________________________                                        Cleansing cream (water-in-oil type):                                          (Compositions)      (weight %)                                                ______________________________________                                         (1) siloxane derivative (E)                                                                      2.0                                                        (2) aluminum monopalmitate                                                                       0.1                                                        (3) sodium citrate 0.7                                                        (4) glycerol monooleate                                                                          2.5                                                        (5) liquid paraffin                                                                              12.0                                                       (6) bleached beeswax                                                                             1.0                                                        (7) petrolatum     1.0                                                        (8) di-2-ethylhexyladipate                                                                       17.0                                                       (9) butyl p-oxybenzoate                                                                          0.2                                                       (10) dibutylhydoxytoluene                                                                          0.01                                                     (11) glycerol       2.0                                                       (12) perfume        0.2                                                       (13) purified water balance                                                   ______________________________________                                    

Preparation

First, ingredients (1) to (10) were mixed and heated to 75° C. and then,while stirring the mixture, previously mixed ingredients (11) and (13)previously heated to 75° C. were gradually added to the mixture to carryout the emulsification. After cooling the mixture, an ingredient (12)was added to the mixture to obtain a cleansing cream.

The obtained cleansing cream was excellent in emulsification stabilityfor a long period of time, and its usage feeling was also excellent.

EXAMPLE 29

    ______________________________________                                        Milk lotion (water-n-oil type):                                               (Compositions)      (weight %)                                                ______________________________________                                         (1) siloxane derivative (N)                                                                      2.0                                                        (2) sodium tartarate                                                                             1.5                                                        (3) sorbitan sesquioleate                                                                        2.0                                                        (4) stearic acid   1.5                                                        (5) olive oil      4.0                                                        (6) liquid paraffin                                                                              4.0                                                        (7) dibutylhydroxytoluene                                                                         0.02                                                      (8) propyl p-oxybenzoate                                                                         0.2                                                        (9) carboxymethylcellulose                                                                       0.1                                                       (10) 1,3-butylene glycol                                                                          5.0                                                       (11) perfume        0.2                                                       (12) purified water balance                                                   ______________________________________                                    

Preparation

First, ingredients (1) to (8) were mixed and heated to 75° C. and then,while stirring the mixture, previously mixed ingredients (0), (10) and(12) previously heated to 75° C. were gradually added to the mixture tocarry out the emulsification. After cooling the mixture, an ingredient(11) was added to the mixture to obtain a milk lotion.

The obtained milk lotion was excellent in emulsification stability for along period of time, and its usage feeling was also excellent.

EXAMPLE 30

    ______________________________________                                        Hair cream (water-in-oil type):                                               (Compositions)     (weight %)                                                 ______________________________________                                        (1) siloxane derivative (A)                                                                      2.0                                                        (2) sodium salicylate                                                                            0.7                                                        (3) liquid paraffin                                                                              5.5                                                        (4) dimethylpolysiloxane                                                                         4.5                                                        (5) glycerol       10.0                                                       (6) perfume        0.1                                                        (7) purified water balance                                                    ______________________________________                                    

Preparation

First, ingredients (1) to (4) were mixed and heated to 75° C., and then,while stirring the mixture, previously mixed ingredients (5) and (7)previously heated to 75° C. were gradually added to the mixture to carryout the emulsification. After cooling the mixture, an ingredient (6) wasadded to the mixture to obtain a hair cream.

The obtained hair cream exhibited excellent emulsification stability.

EXAMPLE 31

    ______________________________________                                        Foundation cream (water-in-oil type):                                         (Compositions)          (weight %)                                            ______________________________________                                         (1) siloxane derivative (N)                                                                          2.0                                                    (2) potassium sorbitanate                                                                             0.05                                                  (3) magnesium sulfate  1.0                                                    (4) polyoxyethylene(7)sorbitoltetraoleate                                                            3.5                                                    (5) liquid paraffin    8.5                                                    (6) volatile silicone  1.0                                                    (7) talc               6.0                                                    (8) Kaolin             8.0                                                    (9) titanium oxide     1.0                                                   (10) iron oxide         0.5                                                   (11) glycerol           8.0                                                   (12) perfume             0.05                                                 (13) purified water     balance                                               ______________________________________                                    

Preparation

First, ingredients (1) to (6) were mixed and heated to 75° C. and then,while stirring the mixture, previously mixed ingredients (11) and (13)previously heated to 75° C. were gradually added to the mixture to carryout the emulsification. Then, ingredients (7) to (10) were added to themixture, and the mixture was uniformly kneaded. After cooling themixture, an ingredient (13) was added to the mixture to obtain afoundation cream.

The obtained foundation cream was excellent in emulsification stabilityfor a long period of time, and its usage feeling was also excellent.

Although the present invention has been described in its preferredembodiments, it is readily understood that the present invention is notrestricted to the preferred embodiments and that various changes andmodifications thereof can be made by those skilled in the art withoutdeparting from the spirit and scope of the present invention.

What is claimed is:
 1. A siloxane of the formula ##STR44## whereinR^(4D) represents an alkyl group having 2 to 30 carbon atoms, t is anumber of 0 to 1,000, w is a number of 1 to 1,000, and v is a number of1 to 1,000.
 2. A cosmetic composition comprising a siloxane of theformula: ##STR45## wherein R^(4D) represents an alkyl group having 2 to30 carbon atoms, t is a number of 0 to 1,000, w is a number of 1 to1,000, and v is a number of 1 to 1,000.
 3. An emulsifyingdermatotherapeutic external agent comprising:(A) 5 to 70 weight % of oilphase component; (B) 20 to 94.9 weight % of water phase component; and(C) 0.1 to 30 weight % of emulsifier including a siloxane of theformula: ##STR46## wherein R^(4D) represents an alkyl group having 2 to30 carbon atoms, t is a number of 0 to 1,000, w is a number of 1 to1,000, and v is a number of 1 to 1,000.
 4. The emulsifyingdermatotherapeutic external agent of claim 3, wherein the oil phasecomponent (A) includes at most 50 weight % of silicone oil.
 5. A methodfor producing a siloxane of the formula: ##STR47## wherein R^(4D)represents an alkyl group having 2 to 30 carbon atoms, t is a number of0 to 1,000, w is a number of 1 to 1,000, and v is a number of 1 to1,000, comprising:reacting a compound of the formula: ##STR48## whereinR^(4D), v, t and w are as above defined with a compound of the formula##STR49##